Contacting fluid solids with gases



Dec. 13,- 1949 w. F. ROLLMAN 2,49l,l3

coxmc'rme mum soLIns wm: GASES 4 Filed April 27, 1948 'To PIZoDucTs QEcovmzv- SYSTEM CAT. HOPPER I vl ii T I :l I H i I IO- I i -15 STIZIPPING 6A5 J 2 I SI'IZIIZENG GAS IQ: 17 i4 15 ZJ oZLcr F. Bellman. {Inventor Patented Dec. 13, i949 UNITED STATES PATENT OFFICE Walter F. Rollman, Cranford, N. 1., assitnor to Standard Oil Development Company, a corporation of Delaware Application April 27, 1948, Serial No. 23,590

4 Claims. 1

The present invention relates to the contactin oi subdivided solid particles with gases. More particularly, the present invention relates to an improved process and an apparatus for contacting solids and gases upflowing at velocities which normally result in substantial attrition and disintegration of such finely divided solids in the conventional type fluid solids reactor. A continuation-in-part of the present application, Serial Number 90,588, filed April 30, 1949, contains claims directed to an apparatus suitable for carrylng out a process disclosed in the present application.

Processes wherein fluidized solids are contacted with gases have several important advantages over other types of gas-solid contacting processes. The fluidized solids operations are characterized by (1) a high degree of intimacy of contact between the gas and the solid particles, (2) a substantial uniformity of temperature throughout the catalyst bed as a result of the rapid circulating of the solids and the accompanying extremely rapid rate of heat transfer from one section of the bed to another and (3) the ease of control of the temperature level of the fluidized bed.

The fluid technique of contacting subdivided solids with gases has found extensive application in many types of chemical processes, both catalytic and non-catalytic, exothermic and endothermic. Among the catalytic processes may be mentioned catalytic cracking of petroleum oils, the synthesis of hydrocarbons from carbon mon oxide and hydrogen by the Fischer process, and the like. Among non-catalytic processes are various reduction reactions, as of ores, carbonization of finely divided carbonaceous material, and the preparation of synthesis gas for the hydrocarbon synthesis reaction.

The fluid technique has proven to be of particu.. lar interest in the catalytic synthesis of hydrocarbons from carbon monoxide and hydrogen, using finely divided catalysts of the iron group. Because of the very high heat release of the reaction, in the neighborhood of 35-50 k. cal./mol of reactant, the improved heat distribution, transfer, and control obtained by the fluid process has made the latter the generally preferred method for carrying out this synthesis. However, advantageous as the fluidized technique has shown itself to be inits application to the hydrocarbon synthesis and other fields, the art as hitherto disclosed has several limitations which have limited the scope of its usefulness, applicability, and emciency in many fields in which it is now employed.

Two of these limitations, which particularly afent in other processes, are the attrition and disintegration oi the catalyst, and the agglomeration resulting from the fusion of both disintegrated and non disintegrated particles into aggregates of non-fluidizable size. These aggregates eventually accumulate to such an extent that they seriously interfere with the fluid operation.

Catalyst disintegration is generall considered to be the result of twocauses, namely (1) mechanical and (2) chemical. Chemical disintegration of an iron type hydrocarbon synthesis catalyst is thought to arise from deposition of carbon within the lattice structure of the catalyst crystal, and this may be controlled by selecting synthesis conditions which minimize carbon formation in the synthesis. Mechanical disintegration, or attrition, however, results from the impact of the fluidized particles with the equipment and with themselves. and is a function Of their turbulence and their velocity.

As disclosed in the art, the fluid solids operation is usually carried out in a reactor in the form of a vertical cylinder, having a screen or grid located in a lower section. The purpose of such screen or grid is to support the dense catalyst bed and to provide suitable distribution for the fluidizing gasiform medium which is admitted from below and passes through the screen or grids. The number of grid openings and their size are such that substantially none of the subdivided solids descend downwardly through the grid.

However, it is a demonstrated fact that attrition using this method of introduction of gas is considerable, largely because of the jet action of the incoming gas. -In order to obtain the desired superficial linear velocity of 0.3 to 5 feet per second for the gases through the reactor bed, a high gas inlet velocity is required, and the jet effect of this gas passing through the distributor oriflces causes a substantial amount of attrition of the catalyst.

Another and allied problem inherent in the use of a perforated plate, screen, or grid as a support for a fluid bed is the problem of insuring complete fiuidization throughout the bed. The channeling action of the gases at the extreme bottom of the reactor results in the formation of a fixed bed resting on the perforated plate. The presence of this fixed, or relatively stationary, bed of catalyst in the immediate vicinity of the grid leads necessarily to poor heat transfer and thus overheating and sintering of catalyst to form agglomerate's 3 which result in poor fluidization and also plug the grid.

The tendency to a fixed bed resting on the perforated plate can be overcome to a certain extent by increasing the number of holes through which the gas is introduced. Beyond a certain point, however, nothing can be gained by. this method because some of the incoming gas, following the path of least resistance, will "shortcircuit" across the top of the grid from one hole to the next. Consequently a tendency to a fixed bed formation immediately above the perforated plate can only be partially corrected at moderate gas velocities by increasing the number of holes. Likewise catalyst attrition is not reduced by increasing the number of orifices in the distributor late.

p Another way to reduce attrition would be to decrease the velocity of the gas through the oriflees. However, it is necessary to use gas velocities high enough to maintain the fluidized catalyst bed in the reactor, and under such conditions the catalyst attrition due to mechanical action is serious.

Furthermore, the fragmented particles, or fines, tend to agglomerate in the system considerably more readily than the particles of fluidizable size, and thus agglomeration resulting from the use of a distributor grid support for the fluidized bed comes about both from the formation of a fixed or stationary bed of fiuidizable particles immediately above said grid, and from the aggregation of fine particles resulting from the attrition of fluidizable particles by the jet action of the gasiform fluidizing medium through the rid.

The present invention overcomes these difl'lculties and afiords additional advantages, the nature of which will be more fully understood from the following description.

It is the principal object of the present invention to provide an improved method and apparatus for carrying out the contactingof solids and gases in a fluidized bed which will not be subject to the limitations mentioned, and will thus permit a wider application of this technique. Another important object of the invention is to carry out high velocity fluid solids operations without excessive attrition of the subdivided solid. Still another object of the invention is to minimize substantially the formation of aggregates of non-fluidizable size within the fluid solids reactor. Other objects and advantages of the invention will become apparent from the description hereinafter.

It has now been found that thorough fluidization of the subdivided solids at the extreme bottom of the reactor can be insured and catalyst attrition minimized by a modification of the manner in which the reaction gases are introduced into the reactor. In accordance with the present invention, the subdivided catalyst in a fluid solids hydrocarbon synthesis reactor is withdrawn continuously through a series of vertical tubes near the periphery near the bottom of the reactor, which tubes connect with a corresponding number of inclined tubes manifolded together at the center of the bottom of the reactor and through which the reactant synthesis at a lower vapor inlet velocity than when catalyst is not recycled, without any tendency to a fixed bed formation ai the extreme bottom of the vessel, thus avoiding any tendency to overheating or sintering of the catalyst as is the case when a distributor grid is present. It has been found by the inventor by laboratory test that catalyst attrition is considerably less, with this mode .of operation wherein the catalyst is carried in suspension at a comparatively high velocity concurrently in a stream of reactant gases, the catalyst then disengaged and returned through vertical tubes to inclined tubes through which the reactant gases flow, thence back to the reactor, than when the synthesis gases are jetted directly into the mass of fluidized catalyst in the conventional manner by passage through a distributor grid. Thus it has been found that with regulated pickup of catalyst in a stream as in the present invention, wherein the catalyst particles are withdrawn from the bed through vertical tubes and discharged for recycle into inclined tubes, turbulence required to insure motion of all of the catalyst in the reactor is minimized, further decreasing attrition.

The invention will best be understood by referring to the accompanying diagrammatic representation of one modification of the present invention. In the description, the operation of the invention will be exemplified by its application to the hydrocarbon synthesis process, though it is to be understood that the invention is applicable to any process involving the contacting of subdivided solids with gases in order to effect physical or chemical changes.

Referring now in detail to the drawing, I is a reactor preferably in the form of a vertical cylinder with a conical base 2 having its apex removed. At the base of said cone a series of inclined tubes 3, 4, etc., converge and discharge directly into I. A synthesis gas feed mixture of H2 and CO in the ratio of about 2 mols Hz to 1 mol CO is introduced into reactor 1 through lines 3 and 4. Lines 3 and 4 are equipped with valves 5 and 6.

Within reaction vessel I a mass of subdivided alkali metal promoted iron catalyst having a particle size distribution such that less than 20% of the particles have diameters 0-20 microns and less than 10% of the particles have diameters larger than 80 microns is maintained in the form of a dense turbulent bed, having a well defined upper level I. This catalyst may be supplied to reactor I from catalyst hopper 8 through line 9, though initially it may be supplied through line It as disclosed below. The superficial velocity of the gases within reactor I are preferably maintained in the range of 0.3 to 1.5 feet per second. Under these conditions the catalyst in the reactor I assumes the form of a turbulent mass, resembling a boiling liquid with a more or less welldefined upper level I and having an apparent density of about 25 to 75 lbs. per cu. ft., dependent upon fluidization conditions. the lower apparent density being associated with the higher velocities. The pressure within the reactor is maintained at from about 200 to about 650 p. s. i. g. depending upon the type conversion product desired, and the temperature within the fluidized mass is kept uniform in the range of ases enter the reactor. The catalyst thus with- 40o-750 F. by appr p t ho s f p adrawn from the reaction zone is picked up by the incoming gases and returned to said zone. The incoming mixture of catalyst and reactant gases passes into the reactor through a cone so ture control, such as internal or external coils (not shown). Volatile reaction products, entrained catalyst, and unreacted synthesis gases are withdrawn through gas-solids separators, such that the turbulent fluid bed condition is arrived as cyclone II, the bulk of the entrained catalyst being returned to the dense bed, and the volatile products and unreacted gases are withdrawn overhead and treated in any manner desired.-

Catalyst is continuously withdrawn from the base of the inverted conical bottom 2 of reactor I through a series of vertical pipes, of which l2 and I3 in the drawing are illustrative, which are located at the periphery of the reactor I. The rate of catalyst flow through these several drawofi' tubes may be controlled by valves H and IS. The catalyst thus withdrawn is discharged into a series of corresponding inclined tubes 3, 4, etc., through which synthesis gas is introduced into reactor l. The catalyst is picked up by the incoming synthesis gas mixture and both are carried concurrently into reactor l.

Above valves l4 and I5, stripping gas may be introduced'through lines l8 and I1. Such stripping gas may comprise steam or tail gas from the system, and its purpose is to remove adsorbed and adhering reaction products from the catalyst. Also, below the point at which the synthesis gases mix with the catalyst, it is preferable to include screens l8 and iii in each gas inlet line 3 and 4 to prevent plugging of the feed gas inlet line when the gas flow is shut off.

When reactor l is started up it may be preferable to feed catalyst into vertical draw-off line l2 through line H) instead of into reactor l proper through line 9.

The embodiment of the invention as illustrated in the diagrammatic representation and. in the foregoing description admits of modifications readily apparent to those skilled in the art, and which are within the scope of the invention. Thus the vertical draw-off tubes maybe extended to the level of the top of the fluidized bed. The drawofl' tubes may be part of a heat exchanger equipment to provide for cooling or heating of the subdivided solids as required with the incoming gases.

The invention is only to be limited by the apously withdrawing downwardly from said reaction zone at least a portion of said finely divided solids in the form of a plurality of substantially vertical moving aerated streams, suspending said solids in a fiuidizing gas, passing separate streams of said gaseous suspensions upwardly along inclined paths corresponding in number to said vertical streams, and uniting said paths in said bottom portion of said reaction zone.

2. The process of claim 1 wherein said solids streams are withdrawn from the periphery of said reaction zone adjacent to said bottom portion.

3. An improved process for converting carbon monoxide and hydrogen to normally liquid hydrocarbons and oxygenated products which comprises contacting carbon monoxide and hydrogen in synthesis proportions at synthesis conditions with a dense, turbulent fluidized mass of finely divided synthesis catalyst in a fluidized solids. reaction zone, which zone comprises a bottom portion the cross sectional area of which increases in an upward direction, withdrawing continuously at least a portion of said catalyst in the form of substantially vertical downwardly flowing streams, said streams being withdrawn from the periphery of the bottom portion of said zone, suspending said withdrawn catalyst in synthesis gas, passing separate streams of said solids suspended in synthesis gas upwardly along inclined path corresponding in number to said vertical streams and uniting said streams in the bottom portion of said reaction zone.

4. The process of claim 3 wherein withdrawn catalyst is stripped of reaction products by a gasiform' stripping agent selected from the class of steam and synthesis gas.

WALTER F. ROLLMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,347,682 Gunness May 2, 1944 2,363,874 Krebs Nov. 28, 1944 2,383,636 Wurth Aug. 28, 1945 

